EP2474563A1 - Polyurethan und Polyharnstoff auf der Basis von Polyisobutylen - Google Patents

Polyurethan und Polyharnstoff auf der Basis von Polyisobutylen Download PDF

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EP2474563A1
EP2474563A1 EP12162484A EP12162484A EP2474563A1 EP 2474563 A1 EP2474563 A1 EP 2474563A1 EP 12162484 A EP12162484 A EP 12162484A EP 12162484 A EP12162484 A EP 12162484A EP 2474563 A1 EP2474563 A1 EP 2474563A1
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primary
terminated
pib
polyisobutylene
terminated polyisobutylene
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EP2474563B1 (de
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Joseph P. Kennedy
Yongmoon Kwon
Subramanyam Ummadisetty
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University of Akron
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Definitions

  • the present invention generally relates to alcohol-terminated polyisobutylene (PIB) compounds, and to a process for making such compounds.
  • the present invention relates to primary alcohol-terminated polyisobutylene compounds, and to a process for making such compounds.
  • the present invention relates to polyisobutylene compounds that can be used to synthesize polyurethanes, to polyurethane compounds made via the use of such polyisobutylene compounds, and to processes for making such compounds.
  • the present invention relates to primary alcohol-terminated polyisobutylene compounds having two or more primary alcohol termini and to a process for making such compounds.
  • the present invention relates to primary terminated polyisobutylene compounds having two or more primary termini selected from amine groups or methacrylate groups.
  • PUs polyurethanes
  • chemical companies e.g., Dow, DuPont, BASF, and Mitsui
  • Polyurethanes are used in a wide variety of industrial and clinical applications in the form of, for example, thermoplastics, rubbers, foams, upholstery, tubing, and various biomaterials.
  • PUs are made by combining three ingredients: (1) a diol (such as tetramethylene oxide); (2) a diisocyanate (such as 4,4'-methylene diphenyl diisocyanate); and (3) an extender (such as 1,4-butane diol).
  • a diol such as tetramethylene oxide
  • a diisocyanate such as 4,4'-methylene diphenyl diisocyanate
  • an extender such as 1,4-butane diol
  • 1,4-butane diol 1,4-butane diol
  • polyurethanes contain a soft (rubbery) and a hard (crystalline) component; and the properties of PUs depend on the nature and relative concentration of the soft/hard components.
  • Binder et al. (see, e.g ., D. Machl, M. J. Kunz and W. H. Binder, Polymer Preprints, 2003, 44(2), p. 85 ) initiated the living polymerization of isobutylene under well-known conditions, terminated the polymer with 1-(3-bromopropyl)-4-(1-phenylvinyl)-benzene, and effected a complicated series of reactions on the product to obtain amine-terminated PIBs. Complex structures very different from those disclosed herein were obtained and the above method did not yield amine-terminated telechelic PIB compounds that carry 1.0 ⁇ 0.05 functional groups.
  • the present invention generally relates to alcohol-terminated polyisobutylene (PIB) compounds, and to a process for making such compounds.
  • the present invention relates to primary alcohol-terminated polyisobutylene compounds, and to a process for making such compounds.
  • the present invention relates to polyisobutylene compounds that can be used to synthesize polyurethanes, to polyurethane compounds made via the use of such polyisobutylene compounds, and to processes for making such compounds.
  • the present invention relates to primary alcohol-terminated polyisobutylene compounds having two or more primary alcohol termini and to a process for making such compounds.
  • the present invention relates to primary terminated polyisobutylene compounds having two or more primary termini selected from amine groups or methacrylate groups.
  • the present invention relates to a method for producing a primary alcohol-terminated polyisobutylene compound comprising the steps of: (A) providing an alkenyl-terminated polyisobutylene having at least two alkenyl termini, wherein the alkenyl termini are formed from straight or branched C 3 to C 12 alkenyl groups having a double bond present at the end of the alkenyl group; (B) subjecting the alkenyl-terminated polyisobutylene to anti-Markovnikov bromination to form a primary bromine-terminated polyisobutylene compound having at least two primary bromine termini; (C) converting the primary bromine-terminated polyisobutylene compound to a primary alcohol-terminated polyisobutylene via a base reaction, the primary alcohol-terminated polyisobutylene having at least two primary alcohol termini; and (D) recovering the primary alcohol-terminated polyisobutylene.
  • the present invention relates to a primary alcohol-terminated polyisobutylene compound according to the following formula: ⁇ C(CH 3 ) 2 -[CH 2 -C(CH 3 ) 2 ] n -R-OH
  • ⁇ represents the remaining portion of a linear, star, hyperbranched, or arborescent molecule
  • n is an integer from 2 to about 5,000
  • R is a straight or branched C 3 to C 12 linkage formed from a corresponding straight or branched C 3 to C 12 alkenyl group having a double bond present at the end of the alkenyl group
  • the primary alcohol-terminated polyisobutylene has at least two primary alcohol termini.
  • the present invention relates to a method for producing a primary methacrylate-terminated polyisobutylene compound comprising the steps of: (a) providing an alkenyl-terminated polyisobutylene having at least two alkenyl termini, wherein the alkenyl termini are formed from straight or branched C 3 to C 12 alkenyl groups having a double bond present at the end of the alkenyl group; (b) subjecting the alkenyl-terminated polyisobutylene to anti-Markovnikov bromination to form a primary bromine-terminated polyisobutylene compound having at least two primary bromine termini; (c) converting the primary bromine-terminated polyisobutylene compound to a primary methacrylate-terminated polyisobutylene via a reaction with at least one alkaline methacrylate compound, the primary methacrylate-terminated polyisobutylene having at least two primary methacrylate termini; and (d) recovering the primary
  • the present invention relates to a primary methacrylate-terminated polyisobutylene compound according to the following formula: ⁇ C(CH 3 ) 2 -[CH 2 -C(CH 3 ) 2 ] n -R-Ma
  • ⁇ represents the remaining portion of a linear, star, hyperbranched, or arborescent molecule
  • n is an integer from 2 to about 5,000
  • R is a straight or branched C 3 to C 12 linkage formed from a corresponding straight or branched C 3 to C 12 alkenyl group having a double bond present at the end of the alkenyl group
  • Ma represents a methacrylate termini
  • the primary methacrylate-terminated polyisobutylene has at least two primary methacrylate termini.
  • the present invention relates to a method for producing a primary amine-terminated polyisobutylene compound comprising the steps of: (i) providing an alkenyl-terminated polyisobutylene having at least two alkenyl termini, wherein the alkenyl termini are formed from straight or branched C 3 to C 12 alkenyl groups having a double bond present at the end of the alkenyl group; (ii) subjecting the alkenyl-terminated polyisobutylene to anti-Markovnikov bromination to form a primary bromine-terminated polyisobutylene compound having at least two primary bromine termini; (iii) converting the primary bromine-terminated polyisobutylene compound to a primary phthalimide-terminated polyisobutylene via a reaction with at least one alkaline phthalimide compound, the primary phthalimide-terminated polyisobutylene having at least two primary phthalimide termini; (iv)
  • the present invention relates to a primary amine-terminated polyisobutylene compound according to the following formula: ⁇ C(CH 3 ) 2 -[CH 2 -C(CH 3 ) 2 ] n -R-NH 2 where ⁇ represents the remaining portion of a linear, star, hyperbranched, or arborescent molecule, n is an integer from 2 to about 5,000, and R is a straight or branched C 3 to C 12 linkage formed from a corresponding straight or branched C 3 to C 12 alkenyl group having a double bond present at the end of the alkenyl group, and where the primary amine-terminated polyisobutylene has at least two primary methacrylate termini.
  • the present invention relates to a method for producing a primary bromine-terminated polyisobutylene compound comprising the steps of: providing an alkenyl-terminated polyisobutylene having at least two alkenyl termini, wherein the alkenyl termini are formed from straight or branched C 3 to C 12 alkenyl groups having a double bond present at the end of the alkenyl group; subjecting the alkenyl-terminated polyisobutylene to anti-Markovnikov bromination to form a primary bromine-terminated polyisobutylene compound having at least two primary bromine termini; and recovering the primary bromine-terminated polyisobutylene.
  • the present invention relates to a primary bromine-terminated polyisobutylene compound according to the following formula: ⁇ C(CH 3 ) 2 -[CH 2 -C(CH 3 ) 2 ] n -R-Br
  • ⁇ represents the remaining portion of a linear, star, hyperbranched, or arborescent molecule
  • n is an integer from 2 to about 5,000
  • R is a straight or branched C 3 to C 12 linkage formed from a corresponding straight or branched C 3 to C 12 alkenyl group having a double bond present at the end of the alkenyl group
  • the primary bromine-terminated polyisobutylene has at least two primary bromine termini.
  • the present invention generally relates to alcohol-terminated polyisobutylene (PIB) compounds, and to a process for making such compounds.
  • the present invention relates to primary alcohol-terminated polyisobutylene compounds, and to a process for making such compounds.
  • the present invention relates to polyisobutylene compounds that can be used to synthesize polyurethanes, to polyurethane compounds made via the use of such polyisobutylene compounds, and to processes for making such compounds.
  • the present invention relates to primary alcohol-terminated polyisobutylene compounds having two or more primary alcohol termini and to a process for making such compounds.
  • the present invention relates to primary terminated polyisobutylene compounds having two or more primary termini selected from amine groups or methacrylate groups.
  • the present invention specifically discloses a method for producing various PIB molecules-terminated with one -CH 2 -CH 2 -CH 2 -OH group
  • the present invention is not limited thereto. Rather, the present invention can be used to produce a wide variety of PIB molecular geometries, where such molecules are-terminated with one or more primary alcohols.
  • the primary alcohols that can be used as terminating groups in the present invention include, but are not limited to, any straight or branched chain primary alcohol substituent group having from 1 to about 12 carbon atoms, or from 1 to about 10 carbon atoms, or from 1 to about 8, or from about 1 to about 6 carbon atoms, or even from about 2 to about 5 carbon atoms.
  • any straight or branched chain primary alcohol substituent group having from 1 to about 12 carbon atoms, or from 1 to about 10 carbon atoms, or from 1 to about 8, or from about 1 to about 6 carbon atoms, or even from about 2 to about 5 carbon atoms.
  • individual range limits can be combined to form alternative non-disclosed range limits.
  • the present invention relates to linear, or star-shaped, or hyperbranched, or arborescent PIB compounds, where such compounds contain one or more primary alcohol-terminated segments.
  • Such molecular geometries are known in the art, and a discussion herein is omitted for the sake of brevity.
  • the present invention relates to star-shaped molecules that contain a center cyclic group (e.g., an aromatic group) to which three or more primary alcohol-terminated PIB arms are attached.
  • the present invention relates to the production and/or manufacture of various PIB compounds and polyurethane compounds made therefrom.
  • the first step involves the polymerization of isobutylene to tert-chlorine-terminated PIB by the 1,3,5-tri(2-methoxyisopropyl)benzene/TiCl 4 system under a blanket of N 2 in a dry-box.
  • a mixed solvent n-hexane/methyl chloride, 60/40 v/v
  • 2,6-di-t-butyl pyridine 0.007 M
  • 1,3,5-tri(2-methoxyisopropyl)benzene 0.044M
  • a 100 mL three-neck flask is charged with heptane (50 mL) and allyltelechelic polyisobutylene (10 grams), and air is bubbled through the solution for 30 minutes at 100°C to activate the allylic end groups. Then the solution is cooled to approximately -10°C and HBr gas is bubbled through the system for 10 minutes.
  • Dry HBr is generated by the reaction of aqueous (47%) hydrogen bromide and sulfuric acid (95 to 98%). After neutralizing the solution with aqueous NaHCO 3 (10%), the product is washed 3 times with water. Finally the solution is dried over magnesium sulfate for at least 12 hours ( i.e ., over night) and filtered. The solvent is then removed via a rotary evaporator. The product is a clear viscous liquid.
  • Figure 1A shows the 1 H NMR spectrum of the allyl-terminated PIB and the primary bromine-terminated PIB product ( Figure 1 B) .
  • the formulae and the group assignments are indicated below for Figures 1A and 1B .
  • n is an integer from 2 to about 5,000, or from about 7 to about 4,500, or from about 10 to about 4,000, or from about 15 to about 3,500, or from about 25 to about 3,000, or from about 75 to about 2,500, or from about 100 to about 2,000, or from about 250 to about 1,500, or even from about 500 to about 1,000.
  • individual range limits can be combined to form alternative non-disclosed range limits.
  • the present invention is not limited to solely the use of allyl-terminated compounds, shown above, in the alcohol-terminated polyisobutylene production process disclosed herein. Instead, other straight or branched C 3 to C 12 , C 4 to C 10 , or even C 5 to C 7 alkenyl groups can be used so long as one double bond in such alkenyl groups is present at the end of the chain.
  • individual range limits can be combined to form alternative non-disclosed range limits.
  • alkenyl groups of the present invention contain only one double bond and this double bond is at the end of the chain as described above.
  • the conversion of the terminal bromine product to a terminal primary hydroxyl group is performed by nucleophilic substitution on the bromine.
  • a round bottom flask equipped with a stirrer is charged with a solution of ⁇ -(PIB-CH 2 -CH 2 -CH 2 -Br) 3 in THF. Then an aqueous solution of NaOH is added, and the charge is stirred for 2 hours at room temperature.
  • a phase transfer catalyst such as tetraethyl ammonium bromide can be added to speed up the reaction.
  • the product is then washed 3 times with water, dried over magnesium sulfate overnight and filtered. Finally the solvent is removed via the use of a rotary evaporator.
  • the product, a primary alcohol-terminated PIB product is a clear viscous liquid.
  • the present invention relates to a process for producing halogen-terminated PIBs (e.g., chlorine-terminated PIBs rather than the bromine containing compounds discussed above). These halogen-terminated PIBs can also be utilized in above process and converted to primary alcohol-terminated PIB compounds. Additionally, as is noted above, the present invention relates to the use of such PIB compounds in the production of polyurethanes, as well as a variety of other polymeric end products, such as methacrylates (via a reaction with methacryloyl chloride), hydrophobic adhesives (e.g ., cyanoacrylate derivatives), epoxy resins, polyesters, etc.
  • halogen-terminated PIBs e.g., chlorine-terminated PIBs rather than the bromine containing compounds discussed above.
  • halogen-terminated PIBs can also be utilized in above process and converted to primary alcohol-terminated PIB compounds.
  • the present invention relates to the use of such PI
  • the primary halogen-terminated PIB compounds of the present invention can be converted into PIB compounds that contain end epoxy groups, amine groups, etc. Previous efforts to inexpensively prepare primary halogen-terminated PIB compounds were fruitless and only resulted in compounds with tertiary terminal halogens.
  • the primary alcohol-terminated PIBs are useful intermediates in the preparation of polyurethanes by reaction via conventional techniques, i.e ., by the use of known isocyanates (e.g ., 4,4'-methylenediphenyl diisocyanate, MDI) and chain extension agents (e.g ., 1,4-butane diol, BDO).
  • isocyanates e.g ., 4,4'-methylenediphenyl diisocyanate, MDI
  • chain extension agents e.g ., 1,4-butane diol, BDO.
  • PUs polyurethanes
  • the primary terminal OH groups can be further derivatized to yield additional useful derivatives. For example, they can be converted to terminal cyanoacrylate groups which can be attached to living tissue and in this manner new tissue adhesives can be prepared.
  • the starting PIB segment can be mono-, di- tri, and multi-functional, and in this manner one can prepare di-terminal, tri-terminal, or other PIB derivatives.
  • the present invention makes it possible to prepare ⁇ , ⁇ di-terminal (telechelic), tri-terminal, or other PIB derivatives.
  • arborescent-PIB arborescent-PIB (arb-PIB) that can carry many primary halogen termini, all of which can be converted to primary alcohol groups.
  • reaction steps can be used to produce a primary alcohol-terminated PIB compound according to the present invention.
  • the present invention relates to primary terminated polyisobutylene compounds having two or more primary termini selected from an amine groups or methacrylate groups.
  • the following embodiments can be applied to linear, star, hyperbranched, or arborescent molecules with the number of repeating units in the PIB portion of such molecules being the same as defined as noted above.
  • the present invention is not limited to solely the use of allyl-terminated compounds in the methacrylate-terminated polyisobutylene production process disclosed herein. Instead, other straight or branched C 3 to C 12 , C 4 to C 10 , or even C 5 to C 7 alkenyl groups can be used so long as one double bond in such alkenyl groups is present at the end of the chain.
  • individual range limits can be combined to form alternative non-disclosed range limits.
  • alkenyl groups of the present invention contain only one double bond and this double bond is at the end of the chain as described above.
  • the synthesis of PIB-(CH 2 ) 3 -NH 2 involves two steps: (a) substitution of the terminal primary bromine to phthalimide-terminated polyisobutylene (PIB-(CH 2 ) 3 -phthalimide); and (b) hydrazinolysis of the phthalimide terminated polyisobutylene to primary amine-terminated polyisobutylene (PIB-(CH 2 ) 3 -NH 2 ).
  • PIB-(CH 2 ) 3 -phthalimide dissolved in a mixture of 20 mL heptane and 20 mL of ethanol is added 3 grams of hydrazine hydrate. This mixture is then refluxed at 105°C for 5 hours. Then the charge is diluted with 50 mL hexanes and washed 3 times with excess water. The organic layer is separated, washed three times with distilled water and dried over MgSO 4 . The hexanes are removed by a rotavap and the polymer is dried under vacuum. The yield of PIB-(CH 2 ) 3 -NH 2 is 0.96 grams.
  • the present invention is not limited to solely the use of allyl-terminated compounds, shown above, in the amine-terminated polyisobutylene production process disclosed herein. Instead other straight or branched C 3 to C 12 , C 4 to C 10 , or even C 5 to C 7 alkenyl groups can be used so long as one double bond in such alkenyl groups is present at the end of the chain.
  • individual range limits can be combined to form alternative non-disclosed range limits.
  • alkenyl groups of the present invention contain only one double bond and this double bond is at the end of the chain as described above.
  • the present invention relates to a polyisobutylenes having at least two primary bromine termini as shown in the formula below: ⁇ C(CH 3 ) 2 -[CH 2 -C(CH 3 ) 2 ] n -R 3 -Br where ⁇ represents the remaining portion of a linear, star, hyperbranched, or arborescent molecule and n is defined as noted above.
  • ⁇ can in some instances represent another bromine atom in order to permit the production of substantially linear di-terminal primary alcohol PIBs.
  • R 3 represents the remainder of the alkenyl group left after subjecting a suitable alkenyl-terminated compound to an anti-Markovnikov bromination step in accordance with the present invention.
  • R 3 could be either a straight or branched C 3 to C 12 , C 4 to C 10 , or even C 5 to C 7 alkyl group (the result of the "starting" alkenyl group having only one double bond, with such double bond being present at the end of the chain as described above).
  • R 3 could be either a straight or branched C 3 to C 12 , C 4 to C 10 , or even C 5 to C 7 alkenyl group (the result of the "starting" alkenyl group having two or more double bonds, with one of the double bonds being present at the end of the chain as described above).
  • PIBs amine-telechelic polyisobutylenes
  • R 4 is as defined below.
  • the present invention relates to alcohol-telechelic PIBs that carry a certain amount of functional primary alcohol end groups (-OH).
  • each and every terminus of a polymer molecule is fitted with a functional end group.
  • the functional end groups of the present invention are hydroxyl or amine end groups.
  • each chain end of a hydroxyl- or an amine-telechelic PIB molecule carries about 1.0 ⁇ 0.05 functional groups ( i.e ., a total of about 2.0 ⁇ 0.05, i.e ., better than about 95 mole percent).
  • PIBs amine-telechelic polyisobutylenes
  • R 4 is selected from linear or branched C 1 to C 20 alkyl group, a linear or branched C 2 to C 20 alkenyl group, a linear or branched C 2 to C 20 alkynyl group.
  • R 4 is selected from linear or branched C 1 to C 10 alkyl group, a linear or branched C 2 to C 10 alkenyl group, a linear or branched C 2 to C 10 alkynyl group, or even C 1 to C 5 alkyl group, a linear or branched C 2 to C 6 alkenyl group, a linear or branched C 2 to C 6 alkynyl group.
  • individual range limits can be combined to form alternative non-disclosed range limits.
  • R 4 is selected from either a methyl, ethyl, propyl, or butyl group, or even a methyl or ethyl group.
  • the simplest telechelic PIB molecule is the ditelechelic structure; for example, a PIB fitted with one -NH 2 group at either end of the molecule: H 2 N-PIB-NH 2 .
  • a PIB carrying only one -NH 2 terminus i.e ., PIB-NH 2
  • PIB-NH 2 is not an amine-telechelic PIB within the definition known to those of skill in the art.
  • a three-arm star amine-telechelic PIB (i.e., a tri-telechelic PIB) carries three -NH 2 groups, one -NH 2 group at each arm end: abbreviated R 5 (PIB-NH 2 ) 3 , where the R 5 is selected from any tri-substituted aromatic group.
  • R 5 in the case of a three-arm star amine-telechelic PIB, R 5 can be any suitable functional group that can be tri-substituted with three PIB-NH 2 groups.
  • a hyperbranched or arborescent amine-telechelic PIB carries many -NH 2 termini, because all the branch ends carry an -NH 2 terminus (multi-telechelic PIB).
  • Molecules with less than about 1.0 ⁇ 0.05 hydroxyl or amine groups per chain end, and synthesis methods that yield less than about 1.0 ⁇ 0.05 hydroxyl or amine groups per chain end are of little or no practical interest in the production of compounds for use in the production of polyurethanes and/or polyureas.
  • This stringent requirement must be met because these telechelic PIBs are designed to be used as intermediates for the production of polyurethanes and polyureas, and precise starting material stoichiometry is required for the preparation of polyurethane and/or polyurea compounds having optimum mechanical properties.
  • precise ( i.e ., about 1.0 ⁇ 0.05) terminal functionality the preparation of high quality polyurethanes and polyureas is not possible.
  • Polymers obtained by the reaction of hydroxy-ditelechelic PIB (i.e ., HO-PIB-OH) and diisocyanates (e.g ., MDI) contain urethane (carbamate) linkages: ⁇ OH + OCN ⁇ ⁇ ⁇ O-CO-NH ⁇ and are called polyurethanes, where in this case --- represents the remainder of the polyurethane molecule.
  • polymers prepared by amine-ditelechelic PIB (H 2 N-PIB-NH 2 ) plus diisocyanates contain urea linkages: ⁇ NH 2 + OCN ⁇ ⁇ ⁇ NH-CO-NH ⁇ and are called polyureas, where in this case ⁇ represents the remainder of the polyurea molecule.
  • the present invention specifically discloses a method for producing various alcohol-telechelic PIBs and amine-telechelic PIBs terminated with at least two alcohol or amine groups
  • the present invention is not limited thereto. Rather, the present invention can be used to produce a wide variety of PIB molecular geometries, where such molecules are terminated with two or more primary alcohols or two or more amine groups be they primary amine groups, secondary amine groups, or tertiary amine groups.
  • the primary alcohols that can be used as terminating groups in the present invention include, but are not limited to, any straight or branched chain primary alcohol substituent group having from 1 to about 12 carbon atoms, or from 1 to about 10 carbon atoms, or from 1 to about 8, or from about 1 to about 6 carbon atoms, or even from about 2 to about 5 carbon atoms.
  • any straight or branched chain primary alcohol substituent group having from 1 to about 12 carbon atoms, or from 1 to about 10 carbon atoms, or from 1 to about 8, or from about 1 to about 6 carbon atoms, or even from about 2 to about 5 carbon atoms.
  • individual range limits can be combined to form alternative non-disclosed range limits.
  • the present invention relates to linear, or star-shaped, or hyperbranched, or arborescent PIB compounds, where such compounds contain two or more primary alcohol-terminated segments, amine-terminated segments, or amine-containing segments.
  • Such molecular geometries are known in the art, and a discussion herein is omitted for the sake of brevity.
  • the present invention relates to star-shaped molecules that contain a center cyclic group (e.g. , an aromatic group) to which three or more primary alcohol-terminated PIB arms are attached, or three or more amine-containing PIB arms are attached.
  • the present invention relates to the production and/or manufacture of various primary alcohol-terminated PIB compounds and polyurethane compounds made therefrom.
  • the first step involves the polymerization of isobutylene to tert-chlorine-terminated PIB by the 1,3,5-tri(2-methoxyisopropyl)benzene/TiCl 4 system under a blanket of N 2 in a dry-box.
  • a mixed solvent n-hexane/methyl chloride, 60/40 v/v
  • 2,6-di-t-butyl pyridine 0.007 M
  • 1,3,5-tri(2-rnethoxyisopropyl)benzene 0.044M
  • a 100 mL three-neck flask is charged with heptane (50 mL) and allyl-telechelic polyisobutylene (10 grams), and air is bubbled through the solution for 30 minutes at 100°C to activate the allylic end groups. Then the solution is cooled to approximately -10°C and HBr gas is bubbled through the system for 10 minutes.
  • Dry HBr is generated by the reaction of aqueous (47%) hydrogen bromide and sulfuric acid (95 to 98%). After neutralizing the solution with aqueous NaHCO 3 (10%), the product is washed 3 times with water. Finally the solution is dried over magnesium sulfate for at least 12 hours ( i.e ., over night) and filtered. The solvent is then removed via a rotary evaporator. The product is a clear viscous liquid.
  • Figure 1A shows the 1 H NMR spectrum of the allyl-terminated PIB and the primary bromine-terminated PIB product ( Figure 1B ).
  • the formulae and the group assignments are indicated below for Figures 1A and 1B .
  • n is an integer from 2 to about 5,000, or from about 7 to about 4,500, or from about 10 to about 4,000, or from about 15 to about 3,500, or from about 25 to about 3,000, or from about 75 to about 2,500, or from about 100 to about 2,000, or from about 250 to about 1,500, or even from about 500 to about 1,000.
  • individual range limits can be combined to form alternative non-disclosed range limits.
  • the present invention is not limited to solely the use of allyl-terminated compounds, shown above, in the alcohol-terminated polyisobutylene production process disclosed herein. Instead, other straight or branched C 3 to C 12 , C 4 to C 10 , or even C 5 to C 7 alkenyl groups can be used so long as one double bond in such alkenyl groups is present at the end of the chain.
  • individual range limits can be combined to form alternative non-disclosed range limits.
  • alkenyl groups of the present invention contain only one double bond and this double bond is at the end of the chain as described above.
  • the conversion of the terminal bromine product to a terminal primary hydroxyl group is performed by nucleophilic substitution on the bromine.
  • a round bottom flask equipped with a stirrer is charged with a solution of ⁇ -(PIB-CH 2 -CH 2 -CH 2 -Br) 3 in THF. Then an aqueous solution of NaOH is added, and the charge is stirred for 2 hours at room temperature.
  • a phase transfer catalyst such as tetraethyl ammonium bromide can be added to speed up the reaction.
  • the product is then washed 3 times with water, dried over magnesium sulfate overnight and filtered. Finally the solvent is removed via the use of a rotary evaporator.
  • the product, a primary alcohol-terminated PIB product is a clear viscous liquid.
  • the present invention relates to a process for producing halogen-terminated PIBs (e.g ., chlorine-terminated PIBs rather than the bromine containing compounds discussed above). These halogen-terminated PIBs can also be utilized in above process and converted to primary alcohol-terminated PIB compounds. Additionally, as is noted above, the present invention relates to the use of such PIB compounds in the production of polyurethanes, as well as a variety of other polymeric end products, such as methacrylates (via a reaction with methacryloyl chloride), hydrophobic adhesives (e.g ., cyanoacrylate derivatives), epoxy resins, polyesters, etc.
  • halogen-terminated PIBs e.g ., chlorine-terminated PIBs rather than the bromine containing compounds discussed above.
  • halogen-terminated PIBs can also be utilized in above process and converted to primary alcohol-terminated PIB compounds.
  • the present invention relates to the use of such
  • the primary halogen-terminated PIB compounds of the present invention can be converted into PIB compounds that contain end epoxy groups, amine groups, etc. Previous efforts to inexpensively prepare primary halogen-terminated PIB compounds were fruitless and only resulted in compounds with tertiary terminal halogens.
  • the primary alcohol-terminated PIBs are useful intermediates in the preparation of polyurethanes by reaction via conventional techniques, i.e. , by the use of known isocyanates (e.g ., 4,4'-methylenediphenyl diisocyanate, MDI) and chain extension agents (e.g ., 1,4-butane diol, BDO).
  • isocyanates e.g ., 4,4'-methylenediphenyl diisocyanate, MDI
  • chain extension agents e.g ., 1,4-butane diol, BDO.
  • PUs polyurethanes
  • the primary terminal OH groups can be further derivatized to yield additional useful derivatives. For example, they can be converted to terminal cyanoacrylate groups which can be attached to living tissue and in this manner new tissue adhesives can be prepared.
  • the starting PIB segment can be mono-, di- tri, and multi-functional, and in this manner one can prepare di-terminal, tri-terminal, or other PIB derivatives.
  • the present invention makes it possible to prepare ⁇ , ⁇ di-terminal (telechelic), tri-terminal, or other PIB derivatives.
  • arborescent-PIB arborescent-PIB (arb-PIB) that can carry many primary halogen termini, all of which can be converted to primary alcohol groups.
  • reaction steps can be used to produce a primary alcohol-terminated PIB compound according to the present invention.
  • n and m are each independently selected from an integer in the range of from 2 to about 5,000, or from about 7 to about 4,500, or from about 10 to about 4,000, or from about 15 to about 3,500, or from about 25 to about 3,000, or from about 75 to about 2,500, or from about 100 to about 2,000, or from about 250 to about 1,500, or even from about 500 to about 1,000.
  • n and m are each independently selected from an integer in the range of from 2 to about 5,000, or from about 7 to about 4,500, or from about 10 to about 4,000, or from about 15 to about 3,500, or from about 25 to about 3,000, or from about 75 to about 2,500, or from about 100 to about 2,000, or from about 250 to about 1,500, or even from about 500 to about 1,000.
  • individual range limits can be combined to form alternative non-disclosed range limits.
  • the above compound can be produced from a corresponding brominated structure as shown above in (C).
  • the following chemical equations summarize the synthesis method for the above compound: where n and m are each independently selected from an integer in the range of from 2 to about 5,000, or from about 7 to about 4,500, or from about 10 to about 4,000, or from about 15 to about 3,500, or from about 25 to about 3,000, or from about 75 to about 2,500, or from about 100 to about 2,000, or from about 250 to about 1,500, or even from about 500 to about 1,000.
  • individual range limits can be combined to form alternative non-disclosed range limits.
  • reaction conditions at A are: 30 grams of polymer, 150 mL of heptane (103 grams), reflux at 110°C for 30 minutes, followed by passing HBr over the polymer solutions for 5 minutes at 0°C.
  • the Allyl-PIB-Allyl is then converted to the telechelic primary bromide, Br-(CH 2 ) 3 -PIB-(CH 2 ) 3 -Br, as described in above.
  • the Br-(CH 2 ) 3 -PIB-(CH 2 ) 3 -Br is converted by using: (1) potassium phthalimide; and (2) hydrazine hydrate to yield the target ditelechelic amine: NH 2 -(CH 2 ) 3 -PIB-(CH 2 ) 3 -NH 2 .
  • the phthalimide-telechelic polyisobutylene (14 grams, 0.0025 moles) is dissolved in 280 mL of heptane, then 280 mL of ethanol and hydrazine hydrate (3.2 grams, 0.1 moles) are added thereto, and the solution is heated to reflux at 110°C for 6 hours.
  • the product is dissolved in hexanes, extracted 3 times with water, dried over magnesium sulfate, and the hexanes are removed by a rotavap.
  • the structure of the target product is ascertained by 1 H NMR spectroscopy.
  • Figure 3 shows the 1 H NMR spectrum of amine-telechelic polyisobutylene together with assignments.
  • HO-PIB-OH The synthesis of HO-PIB-OH is as described above.
  • the polyurethane is obtained by reaction of the HO-PIB-OH with methylene-bis-phenyl isocyanate (MDI).
  • MDI methylene-bis-phenyl isocyanate
  • n and m are each independently selected from an integer in the range of from 2 to about 5,000, or from about 7 to about 4,500, or from about 10 to about 4,000, or from about 15 to about 3,500, or from about 25 to about 3,000, or from about 75 to about 2,500, or from about 100 to about 2,000, or from about 250 to about 1,500, or even from about 500 to about 1,000.
  • individual range limits can be combined to form alternative non-disclosed range limits.
  • the polyurethane product is a pale yellow supple rubbery sheet, soluble in THF. Manual examination reveals good mechanical properties.
  • the weight loss is experimentally determined by removing the pre-weighed samples from the nitric acid, rinsing them thoroughly with water, drying them till weight constancy (approximately 24 hours), and weighed again.
  • a "control" polyurethane prepared using a HO-PDMS-OH and MDI, and with another commercially available polyurethane (AorTech Biomaterials, Batch # 60802, E2A pellets sample).
  • Table 1 summarizes the results of aggressive oxidative degradation test performed with PIB-, PDMS-based polyurethanes and a PIB-based polyurea.
  • the oxidant is 65% HNO 3 at room temperature.
  • TABLE 1 Materials Time of exposure to concentrated HNO 3 Weight Loss in Percent Observations PIB-Based (HO-PIB-OH) Polyurethane 1 hour 0 No visible change 4 hours 0 No visible change 24 hours 0 No visible change 48 hours 0 Deep brown discoloration, sample becomes weak PDMS-based (HO-PDMS-OH) Control Polyurethane 30 minutes 40 Sample disintegrates to pasty mass adhering to glass 2 hours 60 Sample largely dissolved, some discolored jelly mass remains 4 hours 90 Sample largely dissolved, some discolored jelly mass remains Commercial Polyurethane (AorTech) 30 minutes 50 Sample disintegrated, some discolored jelly mass remains 1.5 hours 70 Sample disintegrated, some discolored jelly mass remains 4 hours 95 Sample disintegrated, some discolored jelly mass remains PIB-Based (H
  • the PIB-based polyurethanes and polyureas do not degrade after 24 hours when exposed to concentrated HNO 3 at room temperature. Oxidative resistance is demonstrated by the negligible weight loss of the polyurethane and polyurea films. After 48 hours exposure to concentrated HNO 3 both the PIB-based polyurethane and polyurea films exhibit deep brown discoloration and a visible weakening of the samples.
  • control polyurethane prepared with HO-PDMS-OH/MDI and a commercial polyurethane (i.e., a material considered highly oxidatively stable) completely degrades, and becomes largely soluble in the acid after less than 4 hours of exposure.
  • the spectacular oxidative resistance of the PIB-based polyurethane and polyurethane formed in accordance with the synthesis processes of the present invention is most likely due to the protection of the vulnerable urethane (carbamate) and urea bonds by the inert PIB chains/domains.
  • the PDMS chains/domains cannot impart protection against the attack of the strong oxidizing acid.
  • the oxidative stability of the polyurea is tested by exposing the sample to concentrated HNO 3 at room temperature (see Table 1 above). The last entry in Table 1 shows data relating to this Example. Evidently, the PIB-based polyurea resists oxidation under the harsh conditions detailed above for 24 hours.

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Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2683844C (en) * 2007-04-12 2015-06-02 Joseph P. Kennedy Injectible cyanoacrylate-functionalized polyisobutylenes
CA2691087C (en) * 2007-06-19 2016-04-05 The University Of Akron Singly-terminated polyisobutylenes and process for making same
WO2009158600A1 (en) 2008-06-27 2009-12-30 Cardiac Pacemakers, Inc. Polyisobutylene urethane, urea and urethane/urea copolymers and medical devices containing the same
EP2373356B1 (de) 2008-12-31 2015-03-04 Boston Scientific Scimed, Inc. Copolymere mit polyisobutylen und biologisch abbaubaren polymersegmenten
AU2010203373B2 (en) 2009-01-12 2013-08-01 University Of Massachusetts Lowell Polyisobutylene-based polyurethanes
WO2011022583A1 (en) * 2009-08-21 2011-02-24 Cardiac Pacemakers, Inc. Crosslinkable polyisobutylene-based polymers and medical devices containing the same
US8374704B2 (en) 2009-09-02 2013-02-12 Cardiac Pacemakers, Inc. Polyisobutylene urethane, urea and urethane/urea copolymers and medical leads containing the same
US8644952B2 (en) 2009-09-02 2014-02-04 Cardiac Pacemakers, Inc. Medical devices including polyisobutylene based polymers and derivatives thereof
EP2499200A4 (de) * 2009-11-11 2014-04-30 Univ Akron Polyurethane, polyharnstoffe und/oder polyurethan-polyharnstoffe auf polyisobutylenbasis sowie herstellungsverfahren dafür
CN102666714B (zh) 2009-11-19 2015-04-29 3M创新有限公司 包含合成橡胶和与丙烯酸类聚合物结合的官能化合成橡胶的共混物的压敏粘合剂
CN102666764B (zh) 2009-11-19 2015-09-30 3M创新有限公司 包含与丙烯酸类聚合物氢键结合的官能化聚异丁烯的压敏粘合剂
JP5739007B2 (ja) 2010-12-20 2015-06-24 カーディアック ペースメイカーズ， インコーポレイテッド 導電性ポリマー導体を有するリード及びその製造方法
EP2741809B1 (de) 2011-08-12 2018-08-01 Cardiac Pacemakers, Inc. Verfahren zum beschichten von vorrichtungen mittels elektrospinning und schmelzblasen
WO2013078139A1 (en) 2011-11-23 2013-05-30 Cardiac Pacemakers, Inc. Fibrous matrix coating materials
WO2013151656A1 (en) 2012-04-02 2013-10-10 Medtronic, Inc. Medical leads
US9334343B2 (en) 2012-09-24 2016-05-10 Exxonmobil Chemical Patents Inc. Hydrohalogenation of vinyl-terminated macromonomers and functionalized derivatives
WO2014081916A2 (en) 2012-11-21 2014-05-30 University Of Massachusetts High strength polyisobutylene polyurethanes
CA2900647A1 (en) * 2013-03-04 2014-09-12 The University Of Akron Photochemical preparation of hydroxyl-terminated polyisobutylenes and related methods and uses
US20150025608A1 (en) 2013-07-22 2015-01-22 Cardiac Pacemakers, Inc. Lubricious, biocompatible hydrophilic thermoset coating using interpenetrating hydrogel networks
WO2015053934A1 (en) 2013-10-10 2015-04-16 Medtronic, Inc. Implantable medical devices including a polyether-polyurethane substrate with improved biostability, and methods
WO2016033158A1 (en) * 2014-08-26 2016-03-03 The University Of Akron Synthesis of -s-ch2ch2-oh telechelic polyisobutylenes and their use for the preparation of biostable polyurethanes
WO2017019513A1 (en) 2015-07-25 2017-02-02 Cardiac Pacemakers, Inc. Medical electrical lead with biostable pvdf-based materials
WO2017019474A1 (en) * 2015-07-30 2017-02-02 Henkel IP & Holding GmbH Synthesis of functionalized polyisobutylenes
WO2017099043A1 (ja) * 2015-12-11 2017-06-15 株式会社カネカ （メタ）アクリロイル末端ポリイソブチレン系重合体の製造方法
EP3390482B1 (de) * 2015-12-17 2021-03-03 Cardiac Pacemakers, Inc. Polyisobutylen-polyurethane und medizinprodukte damit
US10465318B2 (en) 2016-12-27 2019-11-05 Boston Scientific Scimed Inc Degradable scaffolding for electrospinning
CN110382568B (zh) 2017-03-07 2022-03-04 心脏起搏器股份公司 烯丙基封端的聚异丁烯的硼氢化/氧化
WO2019036544A1 (en) 2017-08-17 2019-02-21 Cardiac Pacemakers, Inc. PHOTORÉTICULATED POLYMERS FOR IMPROVED DURABILITY
CN107884497B (zh) * 2017-11-17 2020-06-02 唐山三友硅业有限责任公司 氯甲烷干燥用浓硫酸残留可燃物的分析和测定装置及方法
WO2019143629A1 (en) 2018-01-17 2019-07-25 Cardiac Pacemakers, Inc. End-capped polyisobutylene polyurethane
US10882945B2 (en) 2018-03-26 2021-01-05 Medtronic, Inc. Modified polyisobutylene-based polymers, methods of making, and medical devices
CN111748086B (zh) * 2020-07-20 2022-08-05 万华化学(四川)有限公司 聚异丁烯基聚碳酸酯共聚物及其制备方法
US20230287167A1 (en) * 2020-08-06 2023-09-14 The University Of Akron Synthesis of high molecular weight and strength polyisobutylene-based polyurethanes and use thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050054806A1 (en) * 2003-09-05 2005-03-10 Manjari Kuntimaddi Monodisperse telechelic amine-based polyureas for use in golf balls

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2819319A (en) * 1954-08-13 1958-01-07 Pan American Petroleum Corp Production of alcohols by hydrolysis of alkyl bromides
US4342849A (en) * 1979-09-10 1982-08-03 The University Of Akron Novel telechelic polymers and processes for the preparation thereof
US4316973A (en) * 1979-09-10 1982-02-23 The University Of Akron Novel telechelic polymers and processes for the preparation thereof
US4888389A (en) * 1985-02-05 1989-12-19 University Of Akron Amphiphilic polymers and method of making said polymers
US4960938A (en) * 1988-11-02 1990-10-02 Occidental Chemical Corporation Preparing 2-chlorobenzylamine from 2-chlorobenzylchloride via 2-chlorobenzylphthalimide
JPH04132706A (ja) * 1990-09-25 1992-05-07 Nippon Shokubai Co Ltd 水酸基末端テレケリックポリマーの製法
US5260383A (en) * 1991-04-17 1993-11-09 Polysar Rubber Corporation Polyisobutylene based block copolymers
AU4033893A (en) * 1992-04-24 1993-11-29 Polymer Technology Group, Inc., The Copolymers and non-porous, semi-permeable membrane thereof and its use for permeating molecules of predetermined molecular weight range
US5340881A (en) * 1992-11-16 1994-08-23 The University Of Akron Aldehyde-telechelic polyisobutylenes, catalytic method for preparing the same with high conversion and selectivity, and block copolymers made thereform
US5414095A (en) * 1994-01-03 1995-05-09 The Sherwin-Williams Company Anhydride-functional primary alkyl halides
GB9615025D0 (en) 1996-07-17 1996-09-04 Bp Chem Int Ltd Production of substituted polyisobutenes
DE19930910C1 (de) 1999-07-06 2001-01-18 Voith Turbo Kg Innenzahnradpumpe für Reversierbetrieb im geschlossenen hydraulischen Kreislauf
US6365171B1 (en) 1999-11-04 2002-04-02 The University Of Akron Amphiphilic networks, implantable immunoisolatory devices and methods of preparation
DE10247462A1 (de) * 2002-10-11 2004-04-22 Basf Ag Derivate von Polymeren für die permanente Modifizierung von hydrophoben Polymeren
TWI263657B (en) * 2002-12-23 2006-10-11 Kaneka Corp Thermoplastic elastomer composition
DE10303275A1 (de) 2003-01-28 2004-07-29 Basf Ag Funktionalisierung von ungesättigten Isobutenpolymeren durch Hydroborierung
WO2005031246A2 (en) 2003-10-02 2005-04-07 The University Of Western Ontario Less-lethal ammunition projectile
US7388033B2 (en) * 2004-09-21 2008-06-17 Capital Chemical Co. Amine-functionalized polyisobutylenes for improved hydrophobizing microemulsions
WO2006106899A1 (ja) * 2005-03-31 2006-10-12 Kaneka Corporation 変性された熱可塑性樹脂

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050054806A1 (en) * 2003-09-05 2005-03-10 Manjari Kuntimaddi Monodisperse telechelic amine-based polyureas for use in golf balls

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
D. MACHL; M. J. KUNZ; W. H. BINDER, POLYMER PREPRINTS, vol. 44, no. 2, 2003, pages 85
KENNEDY J-P- ET AL.: "Polyisobutylene-Based Diols and Polyurethanes", ACS SYMPOSIUM SERIES - URETHANE CHEMISTRY AND APPLICATIONS, vol. 172, 30 November 1981 (1981-11-30), pages 383 - 391, XP002675704, DOI: 10.1021/bk-1981-0172.ch025 *
LECH WILCZEK; JOSEPH P. KENNEDY, THE JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY, vol. 25, 1987, pages 3255 - 3265
MIYABAYASHI T., KENNEDY J. P.: "Characterization of polyisobutylene-based model urethane networks", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 31, no. 8, 1986, pages 2523 - 2532, XP002675705, DOI: 10.1002/app.1986.070310813 *
PERCEC V ET AL: "NEW TELECHELIC POLYMERS AND SEQUENTIAL COPOLYMERS BY POLYFUNCTIONAL INITIATOR-TRANSFER AGENTS (INIFERS) 29. SYNTHESIS OF ALPHA, OMEGA-DI(AMINO)POLYISOBUTYLENES", POLYMER BULLETIN, SPRINGER, HEIDELBERG, DE, vol. 9, 1 January 1983 (1983-01-01), pages 27 - 32, XP009003445, ISSN: 0170-0839 *

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US20170174796A1 (en) 2017-06-22
US20160090437A1 (en) 2016-03-31
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CA2670786C (en) 2015-06-23
EP2099831B1 (de) 2019-07-31
CN101611065B (zh) 2012-05-02
CN105628897A (zh) 2016-06-01
KR20140066801A (ko) 2014-06-02
CN102603938B (zh) 2015-11-18
US9834622B2 (en) 2017-12-05
US9587067B2 (en) 2017-03-07
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US20100130696A1 (en) 2010-05-27
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US20140005349A1 (en) 2014-01-02
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US8552118B2 (en) 2013-10-08
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US10005852B2 (en) 2018-06-26
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